Catalytically cracked gasoline forms a major part of the gasoline product pool in the United States. It is conventional to recover the product of catalytic cracking and to fractionate the product into various fractions such as light gases; naphtha, including light and heavy gasoline; distillate fractions, such as heating oil and Diesel fuel; lube oil base fractions; and heavier fractions.
A large proportion of the sulfur in gasoline results from the catalytically cracked gasoline component due to the sulfur content of the petroleum fractions being catalytically cracked. The sulfur impurities may require removal, usually by hydrotreating, in order to comply with product specifications or to ensure compliance with environmental regulations both of which are expected to become more stringent in the future, possibly permitting no more than about 300 ppmw sulfur in motor gasolines. Low sulfur levels result in reduced emissions of CO, NO.sub.x and hydrocarbons.
In naphtha hydrotreating, the naphtha is contacted with a suitable hydrotreating catalyst at elevated temperature and somewhat elevated pressure in the presence of a hydrogen atmosphere. One suitable family of catalysts which has been widely used for this service is a combination of a Group VIII and a Group VI element, such as cobalt and molybdenum, on a suitable substrate, such as alumina. After completion of hydrotreating, the product may be fractionated, or flashed, to release the hydrogen sulfide and collect the sweetened gasoline.
However, cracked naphtha, as it comes from the catalytic cracker and without any further treatments, such as purifying operations, has a relatively high octane number as a result of the presence of olefinic components. It also has an excellent volumetric yield. As such, cracked gasoline is an excellent contributor to the gasoline pool. It contributes a large quantity of product at a high blending octane number. In some cases, this fraction may contribute as much as up to half the gasoline in the refinery pool.
Hydrotreating of any of the sulfur containing fractions which boil in the gasoline boiling range causes a reduction in the olefin content, and consequently a reduction in the octane number and as the degree of desulfurization increases, the octane number of the normally liquid gasoline boiling range product decreases. Some of the hydrogen may also cause some hydrocracking as well as olefin saturation, depending on the conditions of the hydrotreating operation.
Proposals have been made for removing sulfur impurities while retaining the high octane contributed by the olefins. Since the sulfur impurities tend to concentrate in the heavy fraction of the gasoline, as noted in U.S. Pat. No. 3,957,625 (Orkin) which proposes a method of removing the sulfur by hydrodesulfurization of the heavy fraction of the catalytically cracked gasoline so as to retain the octane contribution from the olefins which are found mainly in the lighter fraction. In one type of conventional, commercial operation, the heavy gasoline fraction is treated in this way. Alternatively, the selectivity for hydrodesulfurization relative to olefin saturation may be shifted by suitable catalyst selection, for example, by the use of a magnesium oxide support instead of the more conventional alumina.
U.S. Pat. No. 4,049,542 (Gibson), for instance, discloses a process in which a copper catalyst is used to desulfurize an olefinic hydrocarbon feed such as catalytically cracked light naphtha.
In any case, regardless of the mechanism by which it happens, the decrease in octane which takes place as a consequence of sulfur removal by hydrotreating creates a tension between the growing need to produce gasoline fuels with higher octane number and--because of current ecological considerations--the need to produce cleaner burning, less polluting fuels, especially low sulfur fuels. This inherent tension is yet more marked in the current supply situation for low sulfur, sweet crudes.
Other processes for enhancing the octane rating of catalytically cracked gasolines have also been proposed in the past. For example, U.S. Pat. No. 3,759,821 (Brennan) discloses a process for upgrading catalytically cracked gasoline by fractionating it into a heavier and a lighter fraction and treating the heavier fraction over a ZSM-5 catalyst, after which the treated fraction is blended back into the lighter fraction. Another process in which the cracked gasoline is fractionated prior to treatment is described in U.S. Pat. No. 4,062,762 (Howard) which discloses a process for desulfurizing naphtha by fractionating the naphtha into three fractions each of which is desulfurized by a different procedure, after which the fractions are recombined.
Other methods have been proposed for increasing the octane number of the gasoline pool. Naphthas, including light and full range naphthas, may be subjected to catalytic reforming so as to increase their octane numbers by converting at least a portion of the paraffins and cycloparaffins in them to aromatics. Fractions to be fed to catalytic reforming, such as over a platinum type catalyst, also need to be desulfurized before reforming because reforming catalysts are generally not sulfur tolerant. Thus, naphthas are usually pretreated by hydrotreating to reduce their sulfur content before reforming. The octane rating of reformate may be increased further by processes such as those described in U.S. Pat. Nos. 3,767,568 and 3,729,409 (Chen) in which the reformate octane is increased by treatment of the reformate with ZSM-5.
Aromatics are generally the source of high octane number, particularly very high research octane numbers and are therefore desirable components of the gasoline pool. They have, however, been the subject of severe limitations as a gasoline component because of possible adverse effects on the ecology, particularly with reference to benzene. It has therefore become desirable, as far as is feasible, to create a gasoline pool in which the higher octanes are contributed by the olefinic and branched chain paraffinic components, rather than the aromatic components. Light and full range naphthas can contribute a substantial volume to the gasoline pool, but they do not generally contribute significantly to higher octane values without reforming.
We have demonstrated in our prior applications Ser. No. 07/850,106, filed on Mar. 12, 1992, now U.S. Pat. No. 5,346,609, and Ser. No. 07/745,311, filed on Aug. 15, 1991, that zeolite ZSM-5 is effective for restoring the octane loss which takes place when the initial naphtha feed is hydrotreated. When the hydrotreated naphtha is passed over the catalyst in the second step of the process, some components of the gasoline are cracked into lower boiling range materials. If these boil below the gasoline boiling range, there will be a loss in the yield of the gasoline product. However, if the cracking products are within the gasoline boiling range, an increase occurs in the net volumetric yield. To achieve this, it is helpful to increase the end point of the naphtha feed to the extent that this will not result in exceeding the gasoline product end point, or similar restrictions (e.g. T.sub.90, T.sub.95).
Catalysts containing combinations of zeolites have been proposed for the catalytic cracking of petroleum fractions. These combined zeolite catalyst systems have demonstrated improvements in the octane number and overall yield of products of catalytic cracking as described in U.S. Pat. No. 3,758,403. There, a catalyst comprising a large pore size crystalline zeolite (pore size greater than 7 Angstrom units) in admixture with ZSM-5 is utilized as the cracking catalyst. The use of varying amounts of a ZSM-5 zeolite in combination with a larger pore material, specifically an X or Y zeolite cracking catalyst is described in U.S. Pat. Nos. 3,769,202; 3,894,931; 3,894,933; 3,894,934 and 4,309,280. In U.S. Pat. No. 4,911,823 a cracking catalyst comprising a combination of zeolite beta and another zeolite such as an intermediate pore size zeolite, i.e. ZSM-5, is described for improvement in the octane number of cracked naphtha products. The use of a catalyst composition comprising zeolite beta and one or more faujasite-type zeolites in catalytic cracking is described in U.S. Pat. No. 4,740,292. The patent discloses improved octane and increased gasoline plus alkylate yield relative to the conventional faujasite-type cracking catalyst used alone.
However, as previously pointed out, the catalytically cracked products still contain high levels of sulfur impurities. Thus, the tension between octane depletion and hydrodesulfurization, remains.